Abstract Erbium pentaphosphate crystals have been characterized and the structure of the orthorhombic polymorph (type III) determined by X‐rays. It has been found that the orthorhombic samples of ErP 5 O 14 , space group Pnma, crystallize mainly at higher temperatures and usually are much larger than monoclinic crystals, space group C2/c, obtained from lower‐temperature crystallizations. Differences in fluorescence and upconversion properties between orthorhombic and monoclinic polymorphs have been detected.